Substituted 3-aminopyrazoles

ABSTRACT

New and valuable pyrazole derivatives having a good herbicidal action, herbicides containing these compounds as active ingredients, and processes for controlling the growth of unwanted plants with these compounds.

This is a division, of application Ser. No. 951,566, filed Oct. 16, 1978, now U.S. Pat. No. 4,260,775.

The present invention relates to new and valuable pyrazole derivatives having a good herbicidal action, herbicides containing these compounds as active ingredients, and processes for controlling the growth of unwanted plants with these compounds.

It is known that substituted pyrazoles or pyrazolium salts, e.g. 1,2-dimethyl-3,5-diphenylpyrazolium methyl sulfate, can be used as herbicides (German Laid-Open Applications DOS Nos. 2,513,750 and 2,260,485). It is also known that 2-(1-methyl-n-propyl)-4,6-dinitrophenyl acetate (German 1,088,575) or 3-isopropyl-2,1,3-benzothiadiazin-4-on-2,2-dioxide (German 1,542,836) may be used as herbicides.

We have now found that substituted pyrazoles of formula (1) ##STR1## where R¹ denotes hydrogen or lower, unsubstituted or substituted alkyl or acyl, or cyano, alkoxycarbonyl, alkylaminocarbonyl, alkylaminothiocarbonyl, dialkylaminocarbonyl, dialkylaminothiocarbonyl, unsubstituted or substituted benzoyl, alkylsulfonyl, unsubstituted or substituted phenylsulfonyl, unsubstituted or substituted aryloxycarbonyl, arylamino-(thio)-carbonyl or alkylaminosulfonyl,

R² denotes hydrogen or lower unsubstituted or alkoxy-substituted alkyl, or acyl,

R³ denotes unsubstituted alkyl or alkyl substituted by alkoxy, alkylthio, alkoxycarbonyl, cyano, halogen, aryl or a heterocyclic radical, or R³ denotes cycloalkyl, bicycloalkyl, alkenyl, cycloalkenyl, or unsubstituted phenyl or phenyl bearing one or more alkyl, alkoxy, alkylthio, nitro, haloalkyl, haloalkoxy, cyano, halogen, carbalkoxy or hydroxy substituents, or unsubstituted pyridyl or pyridyl substituted in the same way, or R² and R³ together denote unsubstituted or substituted polymethylene which may contain hetero atoms

R⁴ denotes halogen, cyano or the radicals ##STR2## R⁶ denoting unsubstituted or halogen-, alkoxy- or alkylthio-substituted methoxy, propoxy or isopropoxy, or lower unsubstituted or halogen-, alkoxy- or alkylthio-substituted alkyl, or alkylthio, amino, alkylamino or dialkylamino, X denotes oxygen or sulfur, and Me⁺ denotes an equivalent of a cation of the metals Li, Na, K, Mg, Ca, Ba, Al, Fe, Co, Ni, Mn, Cu and Zn, and R⁵ denotes hydrogen or unsubstituted or halogen-, alkylthio-, alkoxy- or alkoxycarbonyl-substituted alkyl, or halogen, alkoxy, hydroxy, alkoxycarbonyl or unsubstituted phenyl or phenyl bearing one or more alkyl, alkoxy, alkylthio, nitro, haloalkyl, cyano, halogen, carbalkoxy or hydroxy substituents, and furthermore, R⁶ denotes ethoxy, in which case R¹ does not simultaneously denote hydrogen, R⁵ does not simultaneously denote methyl, R² does not simultaneously denote hydrogen, and R³ does not simultaneously denote methyl, ethyl or unsubstituted phenyl or phenyl bearing methyl, chlorine or trifluoromethyl in 2-and/or 3-position or R¹ does not simultaneously denote hydrogen, R⁵ does not simultaneously denote methyl, R² does not simultaneously denote methyl and R³ does not simultaneously denote methyl, and R⁶ also denotes hydroxy, in which case R¹ does not simultaneously denote hydrogen, R² does not simultaneously denote hydrogen, R³ does not simultaneously denote unsubstituted phenyl or phenyl bearing methyl or trifluoromethyl in 2- and/or 3-position and R⁵ does not simultaneously denote methyl, and the salts and metal complex compounds thereof, exhibit a good herbicidal action and a selective herbicidal action as regards crop plants and may be used as desiccants in various plants.

The new substituted 3-aminopyrazoles may be in the form of their salts with conventional strong inorganic or organic acids, such as hydrochloric acid, hydrobromic acid, nitric acid, sulfuric acid, tetrafluoboric acid, fluosulfonic acid, formic acid, a halogenated carboxylic acid, e.g. trichloroacetic acid, an alkanesulfonic acid, e.g. methanesulfonic acid, a halogenated alkanesulfonic acid, e.g. trifluomethanesulfonic acid, perfluohexanesulfonic acid, and an arylsulfonic acid, e.g. dodecylbenzenesulfonic acid.

On account of the tautomeric structure, two isomers occur in the starting materials of the new substituted 3-aminopyrazoles: ##STR3##

The isomer ratio is determined substantially by the various substituents. Therefore any formula or name may be understood to be either of the two isomers.

The new substituted 3-aminopyrazoles may be in the form of their metal complex compounds with transition metals, for example copper, iron, zinc, manganese, cobalt and nickel.

R¹ may for example denote the following:

hydrogen, methyl, ethyl, n-propyl, isopropyl, isobutyl, sec-butyl and tert-butyl, formyl, acetyl, propionyl, chloroacetyl, bromoacetyl, trichloroacetyl, trifluoroacetyl, 2,4-dichlorophenoxyacetyl, (2,4-chlorophenoxy)-propionyl, cyano, methoxycarbonyl, ethoxycarbonyl, isopropoxycarbonyl, phenoxycarbonyl, methylaminocarbonyl, isopropylaminocarbonyl, benzoyl, 2',4'-dichlorobenzoyl, methylsulfonyl, ethylsulfonyl, isopropylsulfonyl, phenylsulfonyl, 4-methylphenylsulfonyl, methylaminosulfonyl, isopropylaminosulfonyl, 3-chlorophenoxycarbonyl, 3,4-dichlorophenoxycarbonyl, 3-(methoxycarbonylamino)-phenoxycarbonyl, 2-methyl-4-chlorophenoxycarbonyl, methylaminothiocarbonyl, dimethylamino-(thio)-carbonyl, phenylamino-(thio)-carbonyl, and 3,4-dichlorophenylamino-(thio)-carbonyl.

R² may for example denote the following:

hydrogen, methyl, ethyl, n-propyl; isopropyl, 1-methoxy-2-propyl, formyl, acetyl and chloroacetyl.

R³ may for example denote the following:

methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 3-methyl-2-butyl, pentyl-2, pentyl-3, hexyl-2, hexyl-3, 2-methyl-pentyl-3, 2,4-dimethyl-pentyl-3, 2-ethylhexyl, dodecyl, 1-methoxy-2-propyl, 1-fluoro-2-propyl, 1-chloro-2-propyl, 1,1,1-trifluoro-2-propyl, 1-cyano-2-propyl, 1-methoxycarbonyl-2-propyl, 2-(methoxycarbonyl)-2-propyl, benzyl, α-phenylethyl, β-phenylethyl, 2-(pyrazolyl-1)-ethyl, 2-(imidazolyl-1)-ethyl, 2-(1',2',4'-triazolyl)-ethyl, allyl, buten-1-yl-3, butyn-1-yl-3, 3-methyl-buten-1-yl-3, 3-methyl-butyn-1-yl-3, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, 2-methylcyclohexyl, 2-methoxycyclohexyl, 3-trifluoromethylcyclohexyl, 1,1-dimethoxypropyl-2, phenyl, 2-methylphenyl, 2-fluorophenyl, 3-chloro-4-fluorophenyl, 2,4-dichlorophenyl, 3,5-dichlorophenyl, 3-methoxyphenyl, 2,5-dimethoxyphenyl, 2-cyanophenyl, 2-nitrophenyl, 3-nitrophenyl, 2-methylthiophenyl, 2-trifluoromethylphenyl, 3-trifluoromethylphenyl, 2-methoxycarbonylphenyl, 3-methoxycarbonylphenyl, 2-hydroxyphenyl, 3-hydroxyphenyl, pyridyl-2, pyridyl-3, pyridyl-4,3-fluorophenyl, 2-chlorophenyl, 3,4-difluorophenyl, 2,4-difluorophenyl, 2,5-difluorophenyl, 2,3-dichlorophenyl, 2,5-dichlorophenyl, 2-methyl-3-chlorophenyl, 2-methyl-5-chlorophenyl, 2-methoxy-5-chlorophenyl, 3-tetrafluoroethoxyphenyl, 2-chloro-5-trifluoromethylphenyl, and 2-methoxy-5-methylphenyl.

R⁴ may for example denote the following:

chloro, bromo, cyano, methoxycarbonyl, ethoxycarbonyl, isopropoxycarbonyl, methoxythiocarbonyl, thiomethylcarbonyl, methylthiocarbonyl, acetyl, chloroacetyl, dichloroacetyl, trichloroacetyl, trifluoroacetyl, methoxyacetyl, amino, methylamino, dimethylamino, carboxyl, Na carboxylate, magnesium carboxylate, and manganese carboxylate.

R⁵ may for example denote the following:

hydrogen, methyl, isopropyl, tert-butyl, chloromethyl, methoxymethyl, cyanomethyl, methoxycarbonylmethyl, chloro, bromo, cyano, methoxy, isopropoxy, hydroxy, phenyl, 2-chlorophenyl, 2-methylphenyl, 3-methoxyphenyl, 3-methylthiophenyl, 4-nitrophenyl, 3-trifluoromethylphenyl, 2,4-dichlorophenyl, 3-cyanophenyl, 2-methoxycarbonylphenyl, and 2-hydroxyphenyl.

If R² and R³ together form polymethylene, the latter may contain hetero atoms, e.g. nitrogen, oxygen and sulfur. Together with the nitrogen atom in 3-position of the pyrazole, the following rings are formed for example: ##STR4## tetramethyleneimino, pentamethylenimino, hexamethylenimino, morpholino, thiomorpholino, and piperazino.

The ring formed together with R² and R³ may contain additional substituents such as alkyl, alkoxy, halogen and cyano.

Processes for the production of the new pyrazole derivatives are described for example in Chem. Ber. 98, 259 (1965).

Another method consists in condensing aldehydes, ketones or α-ketocarboxylic acid derivatives with 3-amino-4-alkoxycarbonyl pyrazoles which may be unsubstituted or substituted in 5-position, and subsequently hydrogenating the Schiff bases thus obtained.

The pyrazoles acylated in 1- or 2-position are obtained by subsequent acylation of the 3-aminopyrazole derivatives by conventional methods.

The salts of the new pyrazoles are prepared by reacting the pyrazoles with the acids in a solvent. The metal complex compounds of the new pyrazoles are prepared by reacting the pyrazoles with the metal salts in a solvent.

The processes selected for preparing the new pyrazoles are illustrated by the following Examples.

EXAMPLE 1 3-anilino-4-isopropoxycarbonyl-5-methylpyrazole

35.7 g of isopropyl 2-chloroacetate is added to a suspension of 33.5 g of 4-phenylthiosemicarbazide in 150 ml of tetrahydrofuran. After the mixture has been stirred for 30 minutes it is boiled for a further 30 minutes and then allowed to cool. The precipitated solid is isolated by suction filtering, washed with acetone and the residue is heated in a water/acetone mixture (1:1). After the separated sulfur has been poured off, the whole is allowed to cool and is neutralized with aqueous NaHCO₃, solution and the precipated solid is isolated; m.p. 138°-139° C. (from toluene).

EXAMPLE 2 2-isobutylamino-4-methoxycarbonyl-5-methylpyrazole

15.1 g of methyl 2-chloroacetate is added to a suspension of 14.7 g of 4-isobutylthiosemicarbazide in 150 ml of tetrahydrofuran. The mixture is stirred for 30 minutes and then boiled. After stirring for a further hour at 65° C., the mixture is cooled, the precipitated solid is isolated and washed with acetone. The residue is dissolved hot in water, filtered off from the precipitated sulfur and, after cooling, aqueous ammonia solution is added. After suction filtering and drying the product, 3-isobutylamino-4-methoxycarbonyl-5-methylpyrazole is isolated; m.p. 100°-103° C.

EXAMPLE 3 3-piperidino-4-methoxycarbonyl-5-methylpyrazole

4,4-pentamethylenethiosemicarbazide (m.p. 98°-99° C.) was prepared by the method disclosed in J. pr. Ch. (2) 159, 189 (1941). 32 g of 4,4-pentamethylenethiosemicarbazide is added to 100 ml of tetrahydrofuran (THF) and the whole is mixed with 31 g of methyl 2-chloroacetate. After stirring for one hour at room temperature, the solid formed is suction filtered, washed with acetone and dissolved in H₂ O, and aqueous ammonia solution is added until the alkaline reaction (pH 8). The oil which separates is separated from the sulfur by extraction with CH₂ Cl₂. After being concentrated it is recrystallized from acetone; m.p. 101°-102° C.

EXAMPLE 4 3-anilino-4-acetyl-5-methylpyrazole

50 g of 4-phenylthiosemicarbazide is suspended in 300 ml of tetrahydrofuran and 0.5 ml of concentrated HCl is added. Then 40.4 g of 3-chloroacetyl acetone is allowed to run in all at once and the whole is cooled with an ice-bath. After 12 hours' stirring, the precipitate formed is suction filtered, washed with acetone and then boiled in a water/acetone mixture (1:1). This hot solution is filtered off from the sulfur and neutralized with aqueous ammonia solution. The product is then suction filtered and recrystallized from acetone; m.p. 246°-247° C.

EXAMPLE 5 3-benzylamino-4-ethoxycarbonylpyrazole

21.2 g of benzaldehyde is added to a suspension of 25 g of 3-amino-4-ethoxycarbonylpyrazole in 200 ml of toluene. The whole is boiled while separating water. In 3 hours a total of 5 ml of water collects. After the toluene has been evaporated, 50 ml of methanol and 50 ml of THF are added and, under cooling, 23 g of NaBH₄ is added at 0°-5° C. After 4 hours' at room temperature, the solvent mixture is drawn off; then 200 ml of ice water is added the whole is extracted three times with 150 ml of methylene chloride each time and the extract is dried over Na₂ SO₄. After concentration, an oil remains that is recrystallized from ligroin/toluene; m.p. 99°-100° C.

EXAMPLE 6 2,5-dimethyl-3-anilino-4-methoxycarbonylpyrazole

36.2 g of 2-methyl-4-phenylthiosemicarbazide is dissolved in 200 ml of methanol and 30.2 g of methyl 2-chloroacetate is added. After one hour's stirring, 10 ml of concentrated HCl is added, and the whole is then boiled. After the sulfur has separated, the mixture is allowed to cool, the sulfur is removed and the residue is evaporated.

The crystalline residue is neutralized with aqueous ammonia solution, separated and, after drying, recrystallized from hexane; m.p. 83°-86° C.

The compound 2,5-dimethyl-3-cyclohexylamino-4-methoxycarbonylpyrazole may be prepared analogously; b.p. (0.5 mm Hg) 113°-117° C.

EXAMPLE 7 2-phenyl-3-anilino-4-carboxymethyl-5-methylpyrazole

The same method was used as in Example 6 except that 2,4-diphenylthiosemicarbazide was used and THF as solvent; m.p. 111°-113° C.

The following tables contain some of the compounds that have been obtained according to a process of Examples 1-7.

                                      TABLE 1                                      __________________________________________________________________________      ##STR5##                                                                      __________________________________________________________________________     No.                                                                               R.sup.2                                                                              R.sup.3  R.sup.5 R.sup.6                                                                             m.p. (°C.)                               __________________________________________________________________________     1  H     phenyl   tert.-butyl                                                                            OC.sub.2 H.sub.5                                                                    108-110                                         2  H     phenyl   phenyl  "    143-145                                         3  H     phenyl   4-nitrophenyl                                                                          "    154                                             4  H     sec.-butyl                                                                              methyl  "                                                    5  H     tert.-butyl                                                                             methyl  "                                                    6  H     phenyl   hydrogen                                                                               "                                                    7  H     methyl   phenyl  "                                                    8  H     methyl   4-chlorophenyl                                                                         "                                                    9  H     methyl   tert.-butyl                                                                            "                                                    10 H     phenyl   hydrogen                                                                               OCH.sub.3                                                                           123-124                                         11 H     cyclohexyl                                                                              hydrogen                                                                               "                                                    12 H     tert.-butyl                                                                             hydrogen                                                                               "                                                    13 H     sec.-butyl                                                                              hydrogen                                                                               "                                                    14 H     phenyl   methyl  "    183-185                                         15 H     2-methylphenyl                                                                          methyl  "    175-177                                         16 H     3-methylphenyl                                                                          methyl  "    188-190                                         17 H     4-methylphenyl                                                                          methyl  "    178-179                                         18 H     2-ethylphenyl                                                                           methyl  "    166-167                                         19 H     2,6-dimethyl-                                                                           methyl  "    190                                                      phenyl                                                                20 H     2-methoxy-                                                                              methyl  "    194                                                      phenyl                                                                21 H     3-methoxy-                                                                              methyl  "    173                                                      phenyl                                                                22 H     4-methoxy-                                                                              methyl  "    168-170                                                  phenyl                                                                23 H     2-hydroxy-                                                                              methyl  "                                                             phenyl                                                                24 H     3-hydroxy-                                                                              methyl  "                                                             phenyl                                                                25 H     4-hydroxy-                                                                              methyl  "                                                             phenyl                                                                26 H     2-chlorophenyl                                                                          methyl  "                                                    27 H     3-chlorophenyl                                                                          methyl  "    206-207                                         28 H     4-chlorophenyl                                                                          methyl  "    201-202                                         29 H     2-fluorophenyl                                                                          methyl  "    190-191                                         30 H     3-fluorophenyl                                                                          methyl  "    182-184                                         31 H     4-fluorophenyl                                                                          methyl  "    186-187                                         32 H     2-trifluoro-                                                                            methyl  "    182-183                                                  methylphenyl                                                          33 H     3-trifluoro-                                                                            methyl  "    198                                                      methylphenyl                                                          34 H     2,5-dimethyl-                                                                           methyl  "    233-235                                                  phenyl                                                                35 H     3,5-dimethyl-                                                                           methyl  "    190-193                                                  phenyl                                                                36 H     2,4-dichloro-                                                                           methyl  "    207-210                                                  phenyl                                                                37 H     3,4-dichloro-                                                                           methyl  "    234-236                                                  phenyl                                                                38 H     2,5-dichloro-                                                                           methyl  "    251-253                                                  phenyl                                                                39 H     3,5-dichloro-                                                                           methyl  "                                                             phenyl                                                                40 H     3-chloro-4-                                                                             methyl  "    212                                                      fluorophenyl                                                          41 H     3,4-difluoro-                                                                           methyl  "    204                                                      phenyl                                                                42 H     2-methyl-3-                                                                             methyl  "    224-226                                                  chlorophenyl                                                          43 H     2-methyl-4-                                                                             methyl  "    205-206                                                  chlorophenyl                                                          44 H     2-methyl-5-                                                                             methyl  "    more than                                                chlorophenyl          240                                             45 H     2-nitrophenyl                                                                           methyl  "                                                    46 H     3-cyanophenyl                                                                           methyl  "                                                    47 H     2-hydroxymethyl-                                                                        methyl  "                                                             phenyl                                                                48 H     2-methylthio-                                                                           methyl  "                                                             phenyl                                                                49 H     2-methoxycar-                                                                           methyl  "                                                             bonylphenyl                                                           50 H     2-azaphenyl                                                                             methyl  "                                                    51 H     3-azaphenyl                                                                             methyl  "                                                    52 H     4-azaphenyl                                                                             methyl  "                                                    53 H     2-methyl-3-aza-                                                                         methyl  "                                                             phenyl                                                                54 H     2-methyl-6-aza-                                                                         methyl  "                                                             phenyl                                                                55 H     methyl   methyl  "    155-157                                         56 H     ethyl    methyl  "    143-144                                         57 H     n-propyl methyl                                                       58 H     allyl    methyl  "    128-130                                         59 H     isopropyl                                                                               methyl  "    100-103                                         60 H     2-methylpropen-                                                                         methyl  "                                                             1-yl-3                                                                61 H     3-methylpropen-                                                                         methyl  "                                                             1-yl-3                                                                62 H     propargyl                                                                               methyl  "                                                    63 H     3-methylpropyn-                                                                         methyl  "                                                             1-yl-3                                                                64 H     3,3-dimethyl-                                                                           methyl  "                                                             propyn-1-yl-3                                                         65 H     3,3-dimethyl-                                                                           methyl  "                                                             propen-1-yl-3                                                         66 H     n-butyl  methyl  "    117-118                                         67 H     iso-butyl                                                                               methyl  "    100-103                                         68 H     sec-butyl                                                                               methyl  "    81-83                                           69 H     tert-butyl                                                                              methyl  "    115                                             70 H     pentyl-2 methyl  "    oil                                             71 H     pentyl-3 methyl  "    81-82                                           72 H     1-methyoxy-                                                                             methyl  "    n.sub.D.sup.21 = 1,5122                                  propyl-2                                                              73 H     1,1-dimethoxy-                                                                          methyl  "                                                             propyl-2                                                              74 H     1-methoxycar-                                                                           methyl  "                                                             bonyl-propyl-2                                                        75 H     1-ethoxycar-                                                                            methyl  "                                                             bonyl-propyl-2                                                        76 H     1-cyano- methyl  "                                                             propyl-2                                                              77 H     1-methoxy-                                                                              methyl  "    oil                                                      butyl-2                                                               78 H     3-methoxy-                                                                              methyl  "    107-108                                                  propyl-1                                                              79 H     1,3-dimethoxy-                                                                          methyl  "                                                             propyl-2                                                              80 H     cyclopentyl                                                                             methyl  "    83-85                                           81 H     2-methylcyclo-                                                                          methyl  "                                                             pentyl-1                                                              82 H     cyclohexyl                                                                              methyl  "    90-92                                           83 H     2-methylcyclo-                                                                          methyl  "                                                             hexyl                                                                 84 H     3-methylcyclo-                                                                          methyl  "                                                             hexyl                                                                 85 H     3-trifluoro-                                                                            methyl  "                                                             methylcyclohexyl                                                      86 H     cyclohexylmethyl                                                                        methyl  "    138-140                                         87 H     benzyl   methyl  "    160-161                                         88 H     2-phenylethyl                                                                           methyl  "    181-182                                         89 H     bicyclo[2.2.1]-                                                                         methyl  "    127-130                                                  heptyl-2                                                                       (= norbonyl)                                                          90 H     adamantyl                                                                               methyl  "    202-203                                         91 H     cycloheptyl                                                                             methyl  "                                                    92 H     cyclooctyl                                                                              methyl  "    145-147                                         93 H     phenyl   ethyl   "                                                    94 H     phenyl   isopropyl                                                                              "    103-104                                         95 H     phenyl   tert-butyl                                                                             "                                                    96 H     methyl   tert-butyl                                                                             "                                                    97 H     methyl   phenyl  "    168-169                                         98 methyl                                                                               methyl   methyl  "    118-119                                         99 methyl                                                                               ethyl    methyl  "    oil                                             100                                                                               methyl                                                                               isopropyl                                                                               methyl  "    96 -98                                          101                                                                               methyl                                                                               sec-butyl                                                                               methyl  "    oil                                             102                                                                               methyl                                                                               1-methoxy-                                                                              methyl  "                                                             2-propyl                                                              103                                                                               methyl                                                                               1-methoxy-2-                                                                            methyl  "                                                             butyl                                                                 104                                                                               methyl                                                                               tert-butyl                                                                              methyl  "                                                    105                                                                               methyl                                                                               cyclohexyl                                                                              methyl  "    118-119                                         106                                                                               methyl                                                                               phenyl   methyl  "    oil                                             107                                                                               ethyl ethyl    methyl  "    90-92                                           108                                                                               ethyl cyclohexyl                                                                              methyl  "    109-110                                         109                                                                               ethyl phenyl   methyl  "    oil                                             110                                                                               1-meth-                                                                              phenyl   methyl  "                                                       oxy-2-                                                                         propyl                                                                      111                                                                               iso-  phenyl   methyl  "    91-92                                              propyl                                                                      __________________________________________________________________________     No.                                                                               R.sup. 2 + R.sup.3                                                                            R.sup.5 R.sup.6                                                                             m.p. (°C.)                               __________________________________________________________________________     112                                                                               tetramethylene methyl  OCH.sub.3                                                                           133-134                                         113                                                                               pentamethylene methyl  "    101-102                                         114                                                                               hexamethylene  methyl  "    oil                                             115                                                                               3-oxapentamethylene                                                                           methyl  "    89-90                                           116                                                                               3-iminopentamethylene                                                                         methyl  "                                                    __________________________________________________________________________     No.                                                                               R.sup.2                                                                              R.sup.3  R.sup.5 R.sup.6                                                                             m.p. (°C.)                               __________________________________________________________________________     117                                                                               methyl                                                                               n-butyl  methyl  OCH.sub.3                                                                           oil                                             118                                                                               methyl                                                                               isobutyl methyl  "    oil                                             119                                                                               H     2-methoxy-5-                                                                            methyl  "                                                             nitrophenyl                                                           120                                                                               1-methoxy-                                                                           2-methyl-                                                                               methyl  "                                                       2-propyl                                                                             phenyl                                                                121                                                                               1-methoxy-                                                                           4-methyl-                                                                               methyl  "                                                       2-propyl                                                                             phenyl                                                                122                                                                               methyl                                                                               3-methoxy-                                                                              methyl  "    oil                                                      phenyl                                                                123                                                                               H     phenyl   methyl  methyl                                                                              247                                             124                                                                               H     phenyl   hydrogen                                                                               methyl                                               125                                                                               H     phenyl   trifluoromethyl                                                                        methyl                                               126                                                                               H     2-methoxy-5-                                                                            methyl  OCH.sub.3                                                                           253-254                                                  chlorophenyl                                                          127                                                                               H     sec-butyl                                                                               methyl  methyl                                               128                                                                               H     tert-butyl                                                                              methyl  methyl                                               129                                                                               H     tert-butyl                                                                              methyl  trifluoro-                                                                     methyl                                               130                                                                               H     tert-butyl                                                                              trifluoro-                                                                             methyl                                                                 methyl                                                       131                                                                               H     cyclohexyl                                                                              methyl  methyl                                                                              more than                                                                      250                                             132                                                                               H     2-fluoro-                                                                               methyl  methyl                                                                              250-252                                                  phenyl                                                                133                                                                               H     2-fluoro-                                                                               methyl  methyl                                                        phenyl                                                                134                                                                               H     2-azaphenyl                                                                             methyl  methyl                                               135                                                                               H     3-azaphenyl                                                                             methyl  methyl                                               136                                                                               H     phenyl   methyl  amino                                                                               more than                                                                      250                                             137                                                                               H     phenyl   methyl  methyl-                                                                        amino                                                138                                                                               H     phenyl   methyl  dimethyl-                                                                      amino                                                139                                                                               H     tert-butyl                                                                              methyl  amino                                                140                                                                               H     sec-butyl                                                                               methyl  methyl-                                                                        amino                                                __________________________________________________________________________

EXAMPLE 8 1-acetyl-3-anilino-4-methoxycarbonyl-5-methylpyrazole

23 g of 3-anilino-4-methoxycarbonyl-5-methylpyrazole is dissolved in 51 g of acetic anhydride and brought to the boil. After 15 minutes' boiling the mixture is allowed to cool, poured into ice water and stirred for 30 minutes. The solid which separates is isolated and recrystallized from methanol; m.p. 115°-116° C.

The position of the acetyl group was determined by means of the IR spectrum (CO band at 1720 cm⁻¹).

This result merely rules out that the anilino radical was acetylated. X-ray structural analysis has shown that the acetyl radical is in 1-position of the pyrazole ring.

EXAMPLE 9 1-acetyl-3-cyclohexylamino-4-methoxycarbonyl-5-methylpyrazole

This compound is prepared in a manner analogous to that described in Example 6, except that the starting materials are reacted at room temperature with cooling. The reaction lasts 1 hour; m.p. 140°-142° C.

Further derivatives of pyrazoles which have been obtained by one of the methods of the Examples or other prior art methods are listed in the following Table.

    __________________________________________________________________________      ##STR6##                                                                      No. R.sup.1       R.sup.2                                                                              R.sup.3          R.sup.4                                                                               R.sup.5  m.p.                  __________________________________________________________________________                                                              (°C.)          141 formyl        hydrogen                                                                             phenyl           CO.sub.2 CH.sub.3                                                                     methyl                         142 formyl        "     sec-butyl        "      "                              143 formyl        "     tert-butyl       "      "                              144 acetyl        "     phenyl           "      "        116                   145 chloro-       "     phenyl           "      "        145-147                   acetyl                                                                     146 methyl-       "     "                "      "        201-203                   sulfonyl                                                                   147 methyl-       "     "                "      "        127                       amino-                                                                         carbonyl                                                                   148 tri-          "     "                "      "                                  fluoro-                                                                        acetyl                                                                     149 propionyl     "     "                "      "        120-122               150 benzoyl       "     "                "      "        155-156               151 methoxy-      "     "                "      "        142                       carbonyl                                                                   152 ethoxycar-    "     "                "      "        130-132                   bonyl                                                                      153 acetyl        "     2-methyl-        "      "        145-147                                       phenyl                                                 154 acetyl        "     3-methyl-        "      "        86-89                                         phenyl                                                 155 acetyl        "     2-fluoro-        "      "        144-146                                       phenyl                                                 156 acetyl        "     3-fluoro-        "      "        135-136                                       phenyl                                                 157 acetyl        "     4-fluoro-        "      "        132-134                                       phenyl                                                 158 acetyl        "     sec-butyl        "      "        76-77                 159 acetyl        "     tert-butyl       "      "        120                   160 acetyl        "     cyclopentyl      "      "        96-98                 161 acetyl        "     cyclohexyl       "      "        140-142               162 acetyl        "     norbonyl         "      "        139-142               163 acetyl        acetyl                                                                               cyclohexyl       "      "        110-112               164 acetyl        methyl                                                                               cyclohexyl       "      "        80-82                 165 acetyl        "     phenyl           "      "        88-90                 166 "             hydrogen                                                                             tert-butyl       acetyl "        146                   167 "             methyl                                                                               "                "      "                              168 "             hydrogen                                                                             phenyl           "      "        140-142               169 "             methyl                                                                               "                "      "                              170 "             hydrogen                                                                             2-fluoro-        "      "                                                      phenyl                                                 171 "             "     cyclohexyl       "      "                              172 "             "     tert-butyl       tri-   "                                                                       fluoro-                                                                        acetyl                                173 trifluoro-    "     "                tri-   "                                  acetyl                               fluoro-                                                                        acetyl                                174 methoxy-      "     phenyl           acetyl "                                  carbonyl                                                                   175 methoxy-      "     tert-butyl       meth-  "                                  carbonyl                             oxycar-                                                                        bonyl                                 176 ethoxy-       "     "                meth-  "                                  carbonyl                             oxycar-                                                                        bonyl                                 177 methoxy-      "     "                acetyl "                                  carbonyl                                                                   178 cyano         "     phenyl           "      "                              179 "             "     "                meth-  "                                                                       oxy-                                                                           carbonyl                              180 acetyl        "     "                cyano  "                              181 "             methyl                                                                               ethyl            meth-  "        41-41                                                          oxy-                                                                           carbonyl                              182 "             "     isopropyl        meth-  "        75- 76                                                         oxy-                                                                           carbonyl                              183 "             "     n-butyl          meth-  "                                                                       oxy-                                                                           carbonyl                              184 "             "     iso-butyl        meth-  "                                                                       oxy-                                                                           carbonyl                              185 "             "     sec-butyl        meth-  "        51-53                                                          oxy-                                                                           carbonyl                              186 "             "     tert-butyl       meth-  "                                                                       oxy-                                                                           carbonyl                              187 "             ethyl phenyl           meth-  "        71-72                                                          oxy-                                                                           carbonyl                              188 "             isopropyl                                                                            "                meth-  "                                                                       oxy-                                                                           carbonyl                              189 "             1-methoxy-                                                                           "                meth-  "                                                2-propyl               oxy-                                                                           carbonyl                              190 "             1-methoxy-                                                                           2-methyl-        meth-  "                                                2-propyl                                                                             phenyl           oxy-                                                                           carbonyl                              191 "             1-methoxy-                                                                           4-methyl-        meth-  "                                                2-propyl                                                                             phenyl           oxy-                                                                           carbonyl                              192 "             3-methoxy-                                                                           methyl           meth-  "                                                phenyl                 oxy-                                                                           carbonyl                              193 "             4-methoxy-                                                                           H                meth-  "        126-128                                 henyl                  oxy-                                                                           carbonyl                              194                                                                                 ##STR7##     H     C.sub.4 H.sub.9 sec                                                                             COOCH.sub.3                                                                           CH.sub.3 63                    195 H             H                                                                                     ##STR8##                                                                                        ##STR9##                                                                             CH.sub.3 196                   196 H             H                                                                                     ##STR10##                                                                                       ##STR11##                                                                            CH.sub.3 105-107               197 H             H                                                                                     ##STR12##       COOC.sub.2 H.sub.5                                                                    H                              198 H             H                                                                                     ##STR13##       COOCH.sub.3                                                                           CH.sub.3 oil                   199 H             H     1-methoxy-       dimethyl-                                                                             methyl                                                 propyl           carbamoyl                             200 H             H     3-hydroxy-       CO.sub.2 C.sub.2 H.sub.5                                                              "        215-217                                       phenyl                                                 201 H             H     phenyl           CO.sub.2 CH.sub.3                                                                     phenyl   139-140               202 phenoxy-      H     "                "      methyl   136-138                   carbonyl                                                                   203 acetyl        CH.sub.3                                                                             1-methoxy-       "      "        52-53                                         2-propyl                                               204 H             H     3-fluoro-        "      H        160                                           phenyl                                                 205 H             H     2-fluoro-        "      "                                                      phenyl                                                 206 H             H     3-methoxy-       "      "                                                      phenyl                                                 207 H             H     phenyl           "      methoxy- 125-126                                                               methyl                         208 H             H     phenyl           "      chloro-  156-157                                                               methyl                         209 H             H     phenyl           "      CH.sub.2CO.sub.2 CH.sub.3                                                               156-157               210 H             H     "                "      CO.sub.2 CH.sub.3              211 H             H     tert-butyl       "      Br                             212 H             H     2,3-dichloro-    "      CH.sub.3 253-255                                       phenyl                                                 213 H             H     2,3-dimethyl-    "      "        216-218                                       phenyl                                                 214 H             H     2-cyanophenyl    "      "                              215 H             H     3-nitrophenyl    "      "                              216 H             H     3-methoxy-       "      "                                                      carbonylphenyl                                         217 H             H     2-chloro-5-      "      "        more than                                     trifluoromethyl-                 240                                           phenyl                                                 218 H             H     2,5-dimethoxy-   "      "        180-181                                       phenyl                                                 219 H             H     2-methoxy-5-     "      "        192                                           methylphenyl                                           220 acetyl        H     sec-butyl        COOCH.sub.3                                                                           H        76-77                 223 "             H     phenyl           CO.sub.2 C.sub.3 H.sub.7                                                              CH.sub.3 121                   224 "             H     "                CO.sub.2 CH.sub.3                                                                     CH.sub.2CO.sub.2 CH.sub.3                                                               142-143               225                                                                                 ##STR14##    H     phenyl           "      CH.sub.3 165-166               226 H             H     phenyl           CN     CH.sub.3 221-222               227 H             H     3-methyl-4-      CO.sub.2 CH.sub.3                                                                     CH.sub.3 192-194                                       fluorophenyl                                           228 acetyl        H     3-methyl-4-      "      "        115                                           fluorophenyl                                           229 acetyl        H     2-methyl-4-      "      "        163-164                                       fluorophenyl                                           230 H             H     2-methyl-5-      "      "        230-232                                       fluorophenyl                                           231 acetyl        H     2-methyl-5-      "      "        191-192                                       chlorophenyl                                           232 acetyl        H     3,4-dichloro-    "      "        142-143                                       phenyl                                                 233 acetyl        H     4-methyl-        "      "        130-132                                       phenyl                                                 234 "             H     4-chloro-        "      "        150-153                                       phenyl                                                 235 "             H     α-phenyl-  "      "        92- 93                                        ethyl                                                  236 "             H                                                                                     ##STR15##       "      "        135-136               237 "             H     2,5-dimeth-      "      "        177-178                                       oxyphenyl                                              238 "             H     2-methoxy-5-     "      "        221-223                                       chlorophenyl                                           239 "             H     2,3-dichloro-    "      "        124-125                                       phenyl                                                 240 "             H     2,5-dichloro-    "      "        180-182                                       phenyl                                                 241 "             H     2-trifluoro-     "      "        147-148                                       methylphenyl                                           242 H             H                                                                                     ##STR16##       "      "        153                   243 H             n-C.sub.3 H.sub.7                                                                    n-C.sub.3 H.sub.7                                                                               "      "        56-58                 244 H             H                                                                                     ##STR17##       "      "        oil                   245 H             H                                                                                     ##STR18##       "      "        amorphous glass       246 H             H     2,4-difluoro-    "      "        184-185                                       phenyl                                                 247 H             H     2,5-difluoro-    "      "        222                                           phenyl                                                 248 2,4-di-       H     phenyl           "      "        197-198                   chloro-                                                                        phenoxy-                                                                       acetyl                                                                     249 α-(2,4- H     phenyl           "      "        152-154                   dichloro-                                                                      phenoxy)                                                                       propionyl                                                                  250 H             CH.sub.3                                                                             3-methoxyphenyl  "      "        oil                   251 phenoxy-      H     pentyl-3-        "      "        94-96                     carbonyl                                                                   252 dimethyl-     H     phenyl           "      "        136                       carbonyl                                                                   253                                                                                 ##STR19##    H     "                "      "        165-167               254                                                                                 ##STR20##    H     phenyl           "      "        102                   255 phenoxy-      H     3-methoxyphenyl  "      "        165-166                   carbonyl                                                                   256 p-toluyl-     H     phenyl           "      "                                  sulfonyl                                                                   __________________________________________________________________________

EXAMPLE 10

The sulfur-containing hydrochloride obtained from 14.7 g of 4-tert-butylthiosemicarbazide and 15.1 g of methyl 2-chloroacetate in 200 ml of tetrahydrofuran is suspended in 100 ml of methanol and boiled. On cooling, the solution filtered hot separates the hydrochloride from 3-tert-butylamino-4-methoxycarbonyl-5-methylpyrazole. Colorless crystals, m.p. 178° C.

The following compounds were prepared analogously.

    ______________________________________                                                                                       m.p.                             No.  R.sup.1                                                                              R.sup.2                                                                               R.sup.3                                                                               R.sup.4 R.sup.5                                                                             salt    (°C.)                     ______________________________________                                         221  H     CH.sub.3                                                                              C.sub.2 H.sub.5                                                                       COOCH.sub.3                                                                            CH.sub.3                                                                            hydro-  147-                                                                   chloride                                                                               149                              222  H     CH.sub.3                                                                              2-n-butyl                                                                             COOCH.sub.3                                                                            CH.sub.3                                                                            hydro-  173-                                                                   chloride                                                                               175                              ______________________________________                                    

Application may be effected for instance in the form of directly sprayable solutions, powders, suspensions (including high-percentage aqueous, oily or other suspensions), dispersions, emulsions, oil dispersions, pastes, dusts, broadcasting agents, or granules by spraying, atomizing, dusting, broadcasting or watering. The forms of application depend entirely on the purpose for which the agents are being used; in any case they should ensure a fine distribution of the active ingredient.

For the preparation of solutions, emulsions, pastes and oil dispersions to be sprayed direct, mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, further coal-tar oils, and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons such as benzene, toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes and their derivatives such as methanol, ethanol, propanol, butanol, chloroform, carbon tetrachloride, cyclohexanol, cyclohexanone, chlorobenzene, isophorone, etc., and strongly polar solvents such as dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, water, etc. are suitable.

Aqueous formulations may be prepared from emulsion concentrates, pastes, oil dispersions or wettable powders by adding water. To prepare emulsions, pastes and oil dispersions the ingredients as such or dissolved in an oil or solvent may be homogenized in water by means of wetting or dispersing agents, adherents or emulsifiers. Concentrates which are suitable for dilution with water may be prepared from active ingredient, wetting agent, adherent, emulsifying or dispersing agent and possibly solvent or oil.

Examples of surfactants are: alkali metal, alkaline earth metal and ammonium salts of ligninsulfonic acid, naphthalenesulfonic acids, phenolsulfonic acids, alkylaryl sulfonates, alkyl sulfates, and alkyl sulfonates, alkali metal and alkaline earth metal salts of dibutylnaphthalenesulfonic acid, lauryl ether sulfate, fatty alcohol sulfates, alkali metal and alkaline earth metal salts of fatty acids, salts of sulfated hexadecanols, heptadecanols, and octadecanols, salts of sulfated fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ethers, ethoxylated isooctylphenol, ethoxylated octylphenol and ethoxylated nonylphenol, alkylphenol polyglycol ethers, tributylphenol polyglycol ethers, alkylaryl polyester alcohols, isotridecyl alcohols, fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignin, sulfite waste liquors and methyl cellulose.

Powders, dusts and broadcasting agents may be prepared by mixing or grinding the active ingredients with a solid carrier.

Granules, e.g., coated, impregnated or homogeneous granules, may be prepared by bonding the active ingredients to solid carriers. Examples of solid carriers are mineral earths such as silicic acid, silica gels, silicates, talc, kaolin, Attaclay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, and ureas, and vegetable products such as grain flours, bark meal, wood meal, and nutshell meal, cellulosic powders, etc.

The formulations contain from 0.1 to 95, and preferably 0.5 to 90%, by weight of active ingredient.

The new compounds exhibit herbicidal action and are suitable for removing or suppressing unwanted plant growth in crops or on non-crop land. It is natural that individual active ingredients have varying intensities or differ in their effect on unwanted plants or crop plants. Their influence on unwanted plants is illustrated in the Tables below. The series of experiments were carried out in the greenhouse and in the open.

I. Greenhouse experiments

Plastic flowerpots having a volume of 300 cm³ were filled with a loamy sand containing about 1.5% of humus. The seeds of the test plants according to Table 1, split up into species, were sown shallowly therein. Immediately afterwards, in the case of preemergence treatment, the active ingredients were applied to the surface of the soil. They were suspended or emulsified in water as distributing agent and sprayed onto the soil by means of atomizing nozzles. After the agents had been applied, the pots were lightly sprinkler-irrigated in order to stimulate germination and growth of the plants and at the same time activate the chemical agents. The pots were then covered with transparent plastic hoods until the plants had emerged. The covering effected uniform germination of the test plants, where this was not impaired by the chemicals, and prevented readily volatile active ingredients from evaporating.

For the purpose of the postemergence treatment, the plants were first grown to a height of 3 to 10 cm, depending on their habit, in the pots and then treated. They were not covered. The tests were carried out in a greenhouse, the warmer sections of the greenhouse (25° to 40° C.) being preferred for the warmth-loving species and 15° to 30° C. for those of temperature climates. The experimental period was from 4 to 6 weeks. During this period the plants were tended and their reactions to the various treatments were evaluated. The following tables contain the test substances, the various rates of application in kg/ha of active substance and the species of test plants. Assessment is on a scale of 0 to 100, 0 denoting no damage or normal emergence and 100 denoting no emergence of the plants or complete destruction at least of the parts of the shoots above the ground.

II. Experiments in the open

These were experiments on small plots at locations with loamy sand of pH 5-6 and a humus content of 1 to 1.5%. Postemergence treatments are described which have been carried out on young test plants in the early growth stages up to a height of 5 cm. The weed flora of the most varied species was governed by the time of year (e.g. spring-germinating species and summer-germinating species). The compounds were emulsified or suspended in water as carrier and distribution medium and applied with the aid of a motor-driven plot spray mounted on a hitch. When there was no natural precipitation, the plots were sprinkler-irrigated in order to ensure the germination and growth of the plants. All the experiments lasted several weeks. Then the evaluation was carried out using the scale 0 to 100.

Results

Tables 2 to 13 contain the results of the experiments.

It has become evident that the new 3-aminopyrazole derivatives have interesting herbicidal properties in pre- and postemergence application and differ from the comparative agents.

What is particularly striking is the broad spectrum of action, numerous unwanted broadleaved and grass plants being controlled. In this aspect, in particular, the new compounds offer substantial advantages over the prior art comparative active ingredients.

There are various ways of applying the compounds of the invention.

1. The agents may be used for the selective control of unwanted plants in various crops, including ornamental lawns, e.g. Bermudagrass (Table 6). The latter may be monocotyledonous or dicotyledonous herbaceous crop plants, the agents also coming into direct contact with the leaves or the leaves of the crop plants. However, application techniques may also be used in which spraying equipment is used that enables the agents to be sprayed in such a way that the leaves of sensitive crop plants are not touched if possible and the agents come into contact only with the soil beneath or the unwanted plants growing in it (post-directed or lay-by).

2. The broad spectrum of species from the most varied families that can be controlled also means that the agents are suitable for destroying unwanted broadleaves and grass weeds in woody trees and bushes as well as sugar cane.

3. Furthermore the agents can be used on non-crop areas such as industrial and railroad areas, parking and storage areas, paths, edges of ditches, and forest cutover land. Here it is more a question of the application rate whether the plants are completely eliminated or merely have their growth suppressed and retarded without the plants dying.

4. The compounds tested include those that are suitable for drying green leaves and stems (desiccants). Such agents are used for example for killing potato tops before the mechanical potato harvest, for controlling weeds that break through in ripe cereal fields before the harvest, for accelerating the drying of soya beans before combine harvesting, and for removing green vegetation in cotton which is ready for picking before the harvest.

In view of the variety of application methods the agents of the invention or compositions containing same may be used for removing unwanted plant growth in a large number of crop in addition to those listed in the Tables. The rates of application may vary from 0.1 to 15 kg/ha or more depending on the object to be controlled. The following are examples of crop plants.

    ______________________________________                                         Botanical name     English term                                                ______________________________________                                         Allium cepa        onions                                                      Ananas comosus     pineapple                                                   Arachis hypogaea   peanuts (groundnuts)                                        Asparagus officinalis                                                                             asparagus                                                   Avena sativa       oats                                                        Beta vulgaris spp. altissima                                                                      sugar beets                                                 Beta vulgaris spp. rapa                                                                           fodder beets                                                Beta vulgaris spp. esculenta                                                                      table beets, red beets                                      Brassica napus var. napus                                                                         rape                                                        Brassica napus var. napobrassica                                               Brassica napus var. rapa                                                                          turnips                                                     Brassica rapa var. silvestris                                                  Camellia sinensis  tea plants                                                  Carthamus tinctorius                                                                              safflower                                                   Citrus limon       lemon                                                       Citrus maxima      grapefruits                                                 Citrus reticulata                                                              Citrus sinensis    orange trees                                                Coffea arabica (Coffea canephora,                                              Coffea liberica)   coffee plants                                               Cucumis melo       melons                                                      Cucumis sativus    cucumber                                                    Cynodon dactylon   Bermudagrass in turfs and                                                      lawns                                                       Dauces carota      carrots                                                     Elaeis guineensis  oil palms                                                   Fragaria vesca     strawberries                                                Glycine max        soybeans                                                    Gossypium hirsutum                                                             (Gossypium arboreum                                                            Gossypium herbaceum                                                                               cotton                                                      Gossypium vitifolium)                                                          Helianthus annuus  sunflowers                                                  Helianthus tuberosus                                                           Hevea brasiliensis rubber plants                                               Hordeum vulgare    barley                                                      Humulus lupulus    hop                                                         Ipomoea batatas    sweet potato                                                Lactuca sativa     lettuce                                                     Lens culinaris     lentils                                                     Linum usitatissimum                                                                               flax                                                        Lycopersicon lycopersicum                                                                         tomato                                                      Malus spp.         apple trees                                                 Manihot esculenta  cassava                                                     Medicago sativa    alfalfa (lucerne)                                           Mentha piperita    peppermint                                                  Musa spp.          banana plants                                               Nicotiana tabacum                                                              (N. rustica)       tobacco                                                     Olea europaea      olive trees                                                 Oryza sativa       rice                                                        Panicum miliaceum                                                              Phaseolus lunatus  limabeans                                                   Phaseolus mungo    mungbeans                                                   Phaseolus vulgaris snapbeans, green beans,                                                        dry beans                                                   Pennisetum glaucum                                                             Petroselinum crispum                                                                              parsley                                                     spp. tuberosum                                                                 Picea abies        Norway spruce                                               Abies alba         fire                                                        Pinus spp.         pine trees                                                  Pisum sativum      English peas                                                Prunus avium       cherry trees                                                Prunus domestica   plum trees                                                  Prunus persica     peach trees                                                 Pyrus communis     pear trees                                                  Ribes sylvestre    red currants                                                Ribes uva-crispa                                                               Ricinus communis                                                               Saccharum officinarum                                                                             sugar cane                                                  Secale cereale     rye                                                         Sesamum indicum    Sesame                                                      Solanum tuberosum  Irish potatoes                                              Sorghum bicolor (s. vulgare)                                                                      grain sorghum                                               Sorghum dochna                                                                 Spinacia oleracea  spinach                                                     Theobrome cacao    cacao plants                                                Trifolium pratense red clover                                                  Triticum aestivum  wheat                                                       Vaccinium corymbosum                                                                              blueberry                                                   Vaccinium vitis-idaea                                                                             cranberry                                                   Vicia faba         tick beans                                                  Vigna sinensis  (V. unguiculata)                                                                  cow peas                                                    Vitis vinifera     grapes                                                      Zea mays           Indian corn, sweet corn,                                                       maize                                                       ______________________________________                                    

To further increase the spectrum of action of the new individual active ingredients, to achieve synergistic effects or to improve persistence in the soil, numerous other herbicidal compounds and growth regulators may be used as components for mixtures and combination. Depending on the area of use and the unwanted plants to be controlled, the following substances or similar derivatives are suitable as components:

    ______________________________________                                          ##STR21##                                                                     R               R.sup.1       R.sup.2                                          ______________________________________                                          ##STR22##      NH.sub.2      Cl                                                ##STR23##      NH.sub.2      Br                                                ##STR24##      OCH.sub.3     OCH.sub.3                                         ##STR25##      OCH.sub.3     OCH.sub.3                                         ##STR26##      NH.sub.2      Cl                                                ##STR27##      NHCH.sub.3    Cl                                                ##STR28##      NH.sub.2      Br                                                ##STR29##      NH . CH.sub.3 Cl                                               ______________________________________                                          ##STR30##                                                                     R          R.sup.1       R.sup.2                                               ______________________________________                                                     ##STR31##    H      salts                                          H                                                                                          ##STR32##    CH.sub.3                                                                              salts                                          H                                                                                          ##STR33##    Cl     salts                                          H                                                                                          ##STR34##    F      salts                                          CH.sub.2 OCH.sub.3                                                                         ##STR35##    F      salts                                                      ##STR36##           salts                                                                                 ##STR37##                               ______________________________________                                          ##STR38##                                                                     R      R.sup.1   R.sup.2                                                                               R.sup.3    R.sup.4                                     ______________________________________                                         H      F.sub.3 C H      C.sub.2 H.sub.5                                                                           C.sub.4 H.sub.9                             H      F.sub.3 C H      n . C.sub.3 H.sub.7                                                                       n . C.sub.3 H.sub.7                         H      F.sub.3 C H      CH.sub.2CH.sub.2 Cl                                                                       n . C.sub.3 H.sub.7                         H      SO.sub.2 NH.sub.2                                                                        H      n . C.sub.3 H.sub.7                                                                       n . C.sub.3 H.sub.7                         H      F.sub.3 C H      nC.sub.3 H.sub.7                                                                           ##STR39##                                  H.sub.3 C                                                                             H.sub.3 C H      H                                                                                          ##STR40##                                  ______________________________________                                          ##STR41##                                                                     R               R.sup.1 R.sup.2                                                ______________________________________                                          ##STR42##      H       iC.sub.3 H.sub.7                                       CH.sub.3        H                                                                                       ##STR43##                                              ##STR44##      H                                                                                       ##STR45##                                              ##STR46##      H       iC.sub.3 H.sub.7                                        ##STR47##      H                                                                                       ##STR48##                                              ##STR49##      H       CH.sub.3                                               ______________________________________                                          ##STR50##                                                                     R               R.sup.1     R.sup.2                                            ______________________________________                                          ##STR51##      H           CH.sub.3                                            ##STR52##      H           C.sub.2 H.sub.5                                     ##STR53##      CH.sub.3    CH.sub.3                                            ##STR54##      H           CH.sub.3                                           ______________________________________                                          ##STR55##                                                                     R            R.sup.1     R.sup.2                                               ______________________________________                                         iC.sub.3 H.sub.7                                                                            iC.sub.3 H.sub.7                                                                           CH.sub.2CClCCl.sub.2                                  iC.sub.3 H.sub.7                                                                            iC.sub.3 H.sub.7                                                                           CH.sub.2CClCHCl                                       n . C.sub.3 H.sub.7                                                                         n . C.sub.3 H.sub.7                                                                        C.sub.2 H.sub.5                                       ______________________________________                                          ##STR56##                                                                     R                 X      Y      R.sup.1                                        ______________________________________                                         CH.sub.3          Cl     Cl     Na                                              ##STR57##        Cl H   Cl CH.sub.3                                                                           Na CH.sub.3                                     ##STR58##        H      CH.sub.3                                                                               ##STR59##                                      ##STR60##        H      CH.sub.3                                                                              Na                                              ##STR61##        H      CH.sub.3                                                                              Na                                             ______________________________________                                          ##STR62##                                                                     R            R.sup.1        R.sup.2                                            ______________________________________                                          ##STR63##   H                                                                                              ##STR64##                                          ##STR65##   H              C.sub.2 H.sub.5                                     ##STR66##                                                                                   ##STR67##     CH.sub.2 Cl                                         ##STR68##                                                                                   ##STR69##     CH.sub.2 Cl                                         ##STR70##   CH.sub.2OCH.sub.3                                                                             CH.sub.2 Cl                                         ##STR71##                                                                                   ##STR72##     CH.sub.2 Cl                                         ##STR73##   iC.sub.3 H.sub.7                                                                              CH.sub.2 Cl                                         ##STR74##   CH.sub.2CH.sub.2OCH.sub.3                                                                     Cl.sub.2 Cl                                        C.sub.2 H.sub.5                                                                             C.sub.2 H.sub.5                                                                                ##STR75##                                          ##STR76##   H                                                                                              ##STR77##                                          ##STR78##   H              CH.sub.3                                            ##STR79##   H              CH.sub.3                                           ______________________________________                                          ##STR80##                                                                     R       R.sup.1   X         R.sup.2                                                                               R.sup.3                                     ______________________________________                                         H       C.sub.2 H.sub.5                                                                          SCH.sub.3 H      C.sub.2 H.sub.5                             H       iC.sub.3 H.sub.7                                                                         SCH.sub.3 H      C.sub.2 H.sub.5                             H       iC.sub.3 H.sub.7                                                                         Cl        H      C.sub.2 H.sub.5                             H       iC.sub.3 H.sub.7                                                                         Cl        H                                                                                      ##STR81##                                  H       C.sub.2 H.sub.5                                                                          Cl        H      C.sub.2 H.sub.5                             H       C.sub.2 H.sub.5                                                                          Cl        H                                                                                      ##STR82##                                  H       iC.sub.3 H.sub.7                                                                         OCH.sub.3 H      iC.sub.3 H.sub.7                            ______________________________________                                          ##STR83##                                                                     X           Y         R                                                        ______________________________________                                         Br          Br        Hsalts                                                   I           I         Hsalts                                                   Br          Br                                                                                        ##STR84##                                                ##STR85##                                                                      ##STR86##                                                                     ______________________________________                                          ##STR87##                                                                     R               R.sup.1 R.sup.2 R.sup.3                                        ______________________________________                                          ##STR88##      H       CH.sub.3                                                                               CH.sub.3                                        ##STR89##      H       CH.sub.3                                                                               CH.sub.3                                        ##STR90##      H       CH.sub.3                                                                               CH.sub.3                                        ##STR91##      CH.sub.3                                                                               CH.sub.3                                                                               H                                               ##STR92##      H       CH.sub.3                                                                               CH.sub.3                                        ##STR93##      H       CH.sub.3                                                                               CH.sub.3                                        ##STR94##      H       CH.sub.3                                                                                ##STR95##                                      ##STR96##      H       CH.sub.3                                                                               OCH.sub.3                                       ##STR97##      H       CH.sub.3                                                                               CH.sub.3                                        ##STR98##      H       CH.sub.3                                                                               CH.sub.3                                        ##STR99##      H       CH.sub.3                                                                               OCH.sub.3                                       ##STR100##     H       CH.sub.3                                                                               CH.sub.3                                        ##STR101##     H       CH.sub.3                                                                               CH.sub.3                                        ##STR102##     H       CH.sub.3                                                                               OCH.sub.3                                       ##STR103##     H       CH.sub.3                                                                               H                                               ##STR104##     CH.sub.3                                                                               CH.sub.3                                                                               H                                               ##STR105##     CH.sub.3                                                                               CH.sub.3                                                                               H                                               ##STR106##     H       C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                 ##STR107##     H       CH.sub.3                                                                               CH.sub.3                                        ##STR108##                                                                    ______________________________________                                          ##STR109##                                                                    R         R.sup.1   R.sup.2  R.sup.3                                           ______________________________________                                         Cl        CF.sub.3  H        COOHsalts                                         Cl        Cl        H        H                                                 Cl        Cl        H                                                                                        ##STR110##                                       H         CF.sub.3  Cl       OC.sub.2 H.sub.5                                   ##STR111##                                                                    ______________________________________                                          ##STR112##                                                                    R                R.sup.1    R.sup.2                                            ______________________________________                                         tert.C.sub.4 H.sub.9                                                                            NH.sub.2   SCH.sub.3                                           ##STR113##      NH.sub.2   CH.sub.3                                            ##STR114##      NH.sub.2   SCH.sub.3                                           ##STR115##                                                                    ______________________________________                                          ##STR116##                                                                    R          R.sup.1   R.sup.2   R.sup.3                                         ______________________________________                                         H          CH.sub.3  Br                                                                                        ##STR117##                                     H          CH.sub.3  Br        iC.sub.3 H.sub.7                                H          CH.sub.3  Cl        tert.C.sub.4 H.sub.9                            H          CH.sub.3  Cl                                                                                        ##STR118##                                      ##STR119##                                                                    ______________________________________                                          ##STR120##                                                                    X               Y           R                                                  ______________________________________                                         CF.sub.3        H           CH.sub.3                                           H               F           CH.sub.3                                            ##STR121##                                                                     ##STR122##                                                                     ##STR123##                                                                    ______________________________________                                          ##STR124##                                                                    R   R.sup.1                                                                              R.sup.2 R.sup.3                                                                              R.sup.4                                                ______________________________________                                         H   Cl    NH.sub.2                                                                               Cl    H         salts, esters, amides                        Cl  Cl    H       Cl    Na                                                     Cl  H     Cl      OCH.sub.3                                                                            H         salts, esters, amides                        Cl  Cl    H       Cl    H . (CH.sub.3).sub.2 NH                                ______________________________________                                          ##STR125##                                                                    R           R.sup.1  R.sup.2                                                   ______________________________________                                          ##STR126## CH.sub.3 H       salts, esters, amides                              ##STR127## H        H       salts, esters, amides                              ##STR128## H        H       salts, esters, amides                              ##STR129## H        H       salts, esters, amides                              ##STR130## CH.sub.3 H       salts, esters, amides                              ##STR131## CH.sub.3 H       salts, esters, amides                              ##STR132## H        H       salts, esters, amides                             ______________________________________                                          ##STR133##                                                                    R               R.sup.1                                                        ______________________________________                                          ##STR134##     H       salts, esters, amides                                   ##STR135##     H       salts, esters, amides                                   ##STR136##                                                                     ##STR137##                                                                     ##STR138##                                                                     ##STR139##                                                                     ##STR140##                                                                     ##STR141##                                                                     ##STR142##                                                                    ______________________________________                                          ##STR143##                                                                    R               R.sup.1       R.sup.2                                          ______________________________________                                         COOCH.sub.3     COOCH.sub.3   Cl                                                ##STR144##     R = CN R = CSNH.sub.2                                           ##STR145##                                                                    ______________________________________                                          ##STR146##                                                                    R               R.sup.1      R.sup.2                                           ______________________________________                                         OH              CH.sub.3     Na                                                CH.sub.3        CH.sub.3     Na                                                CH.sub.3        CH.sub.3     OH                                                ONa             CH.sub.3     Na                                                 ##STR147##                                                                     ##STR148##                                                                     ##STR149##                                                                     ##STR150##                                                                     ##STR151##                                                                     ##STR152##                                                                     ##STR153##                                                                     ##STR154##                                                                     ##STR155##                                                                     ##STR156##                                                                     ##STR157##                                                                     ##STR158##                                                                     ##STR159##                                                                     ##STR160##                                                                    ______________________________________                                    

It is also advantageous to apply the compounds of the invention either alone or in combination with other herbicides, in admixture with other crop protection agents, for example agents for combatting pest or phytopathogenic fungi or bacteria. Of further interest is the fact that the compounds of the invention may be mixed with solutions of mineral fertilizers used to eliminate trace element or nutritional deficiencies.

Spreader-stickers and non-phytothoxic oils may be added to the compounds of the invention to ensure that they take effect. ##STR161##

                  TABLE 1                                                          ______________________________________                                         List of test plants                                                            Botanical name    English term                                                 ______________________________________                                         Abutilon theoprasti                                                                              velvet leaf                                                  Amaranthus retroflexus                                                                           redroot pigweed                                              Carthamus tinctorius                                                                             safflower                                                    Chenopodium album lambsquarters (goosefoot)                                    Centaurea cyanus  cornflower                                                   Cynodon dactylon  Bermudagrass                                                 Cyperus difformis smallflower umbrellaplant                                    Datura stramonium Jimsonweed                                                   Daucus carota     carrots                                                      Echinochloa crus galli                                                                           barnyardgrass                                                Euphorbia geniculata                                                                             Southamerican member of the                                                    spurge family                                                Galium aparine    catchweed bedstraw                                           Helianthus annuus sunflower                                                    Ipomoea spp.      morningglory                                                 Lamium purpureum  red deadnettle                                               Lolium multiflorum                                                                               annual raygrass                                              Matricaria spp.   chamomile                                                    Mercurialis annua annual mercury                                               Pisum sativum     English peas                                                 Polygonum percicaria                                                                             ladystumb                                                    Polygonum aviculare                                                                              prostrate knotweed                                           Raphanus raphanistrum                                                                            wild radish                                                  Sesbania exaltata hemp sesbania                                                Setaria spp.      foxtail spp.                                                 Sida spinosa      teaweed (prickly sida)                                       Sinapis alba      white mustard                                                Sinapis arvensis  yellow charlock                                              Solanum nigrum    black nightshade                                             Sorghum bicolor   Sorghum                                                      Sorghum halepense Johnsongrass                                                 Stellaria media   chickweed                                                    Triticum aestivum wheat                                                        Xanthium pensylvanicum                                                                           common cocklebur                                             Zea mays          Indian corn                                                  Alopecurus myosuroides                                                                           slender foxtail                                              Arachis hypogaea  peanut (groundnuts)                                          Fragaria vesca    strawberries                                                 Gossypium hirsutum                                                                               cotton                                                       Lamium amplexicaule                                                                              henbit                                                        Portulaca oleracea                                                                              purslane                                                     ______________________________________                                    

                                      TABLE 2                                      __________________________________________________________________________     Herbicidal action of compounds on unwanted plants;                             preemergence treatment in the greenhouse                                                 Test plants and % damage                                             Compound  Echinochloa                                                                           Euphorbia                                                                            Ipomoea                                                                             Solanum                                                                             Sorghum                                       no.   kg/ha                                                                              crus galli                                                                            geniculata                                                                           spp. nigrum                                                                              halepense                                     __________________________________________________________________________     14    4.0 100     75   85   95   85                                            68    2.0  70    100   93   --   70                                            106   4.0 100    100   100  40   100                                           144   4.0 100    100   100  80   75                                            149   4.0 100    100   90   90   75                                            113   4.0  60    --    75   50   60                                                      Setaria spp.                                                         29    4.0  40    --    95   90   20                                            59    4.0 100    --    100  95   90                                            80    4.0 100    --    100  95   100                                           89    4.0 100    --    100  95   70                                            69    4.0 100    --    100  75   95                                            __________________________________________________________________________      0 = no damage                                                                  100 = plants completely destroyed                                        

                                      TABLE 3                                      __________________________________________________________________________     Herbicidal action; postemergence treatment in the greenhouse                                             Test plants and % damage                             Compound                  Abutilon                                                                             Echinochloa                                                                           Datura                                                                                Setaria                                                                           Sida                                                                               Solanum                   no.                   kg/ha                                                                              theophrasti                                                                          crus galli                                                                            stramonium                                                                           spp.                                                                               spinosa                                                                            nigrum                    __________________________________________________________________________     29                    1.0 100   0      100   100 100 100                                             2.0 100   30     100   100 100 100                       59                    1.0 100   40     40    --  50  40                                              2.0 100   65     60    --  70  100                       80                    1.0 100   --     40    100 20  50                                              2.0 100   75     100   100 100 100                       89                    1.0 100   75     100   100 80  100                                             2.0 100   75     100   100 100 100                       prior art A                                                                          ##STR162##      1.0 2.0                                                                            15 18 0 0    32 48  0 20                                                                              7 25                                                                               65 70                     prior art B                                                                          ##STR163##      1.0 2.0                                                                            100 100                                                                              0 0    100 100                                                                              0 30                                                                               100 100                                                                            100 100                   __________________________________________________________________________      0 = no damage                                                                  100 = plants completely destroyed                                        

                                      TABLE 4                                      __________________________________________________________________________     Herbicidal action; postemergence application in the greenhouse                           Test plants and % damage                                             Compound  Centaurea                                                                            Echinochloa                                                                            Galium                                                                             Ipomoea                                                                             Lolium                                                                               Polygonum                               no.   kg/ha                                                                              cyanus                                                                               crus galli                                                                             aparine                                                                            spp. multiflorum                                                                          aviculare                               __________________________________________________________________________     67    3.0 100   100     0   100  100   0                                       15    3.0 100   100     100 100  100   0                                       71    3.0 100   100     30  100  100   100                                     70    3.0 100   100     30  100  100   100                                     31    3.0 50    100     50  100  0     100                                     77    3.0 100   --      50  100  50    0                                       161   3.0 100   100     100 60   100   100                                     115   3.0 100   50      0   100  100   100                                     132   3.0 50    100     0   0    100   --                                      157   3.0 100   100     100 100  70    0                                       160   3.0 100   100     70  100  100   100                                     154   3.0 100   100     100 100  70    0                                       105   3.0 100   100     0   100  100   30                                      164   3.0 100   70      100 100  100   30                                      165   3.0 100   100     50  100  100   100                                     162   3.0 100   100     100 100  100   30                                      21    3.0 100   100     0   100  70    0                                       100   3.0 100   80      0   100  100   --                                      159   3.0 100   90      100 100  100   100                                     166   3.0 100   40      70  90   95    --                                      72    3.0 100   40      20  70   95    --                                      204   3.0 40    100     40  0    90    --                                      158   3.0 100   40      95  40   100   --                                      10    3.0 100   80      100 100  100   --                                      111   3.0 40    20      100 40   100   --                                      187   3.0 20    40      100 90   100   --                                      101   3.0 100   40      100 100  100   --                                      221   3.0 90    0       90  0    0     --                                      109   3.0 80    40      100 100  100   --                                      168   3.0 100   100     40  0    100   0                                       222   3.0 100   60      100 95   --    --                                      185   3.0 100   35      95  95   --    --                                      __________________________________________________________________________      0 = no damage                                                                  100 = completely destroyed                                               

                                      TABLE 5                                      __________________________________________________________________________     Herbicidal action; postemergence treatment in the open                                             Test plants and % damage                                                                                Raphanus                                                                       raphanistrum/                     Compound            Chenopodium                                                                           Matricaria                                                                           Polygonum                                                                            Polygonum                                                                            Sinapis                                                                               Stellaria                  no.             kg/ha                                                                              album  spp.  convolvulus                                                                          persicaria                                                                           arvensis                                                                              media                      __________________________________________________________________________     14              2.0 80     20    30    --    70     70                                         4.0 90     40    50    --    80     95                         194             2.0 98     68    70    65    80     98                                         4.0 100    88    95    95    98     100                        68              2.0 100    90    --    75    85     100                                        4.0 100    98    --    80    90     100                        82              2.0 98     50    90    60    80     95                                         4.0 100    95    100   --    100    100                        106             2.0 100    65    90    --    90     85                                         4.0 100    90    100   --    100    95                         144             2.0 100    60    95    --    95     100                                        4.0 100    90    100   --    100    100                        149             2.0 100    60    100   --    100    100                                        4.0 100    80    100   --    100    100                        123             2.0 100    15    --    75    --     95                                         4.0 100    20    --    90    --     100                        30              2.0 100    20    --    80    --     100                                        4.0 100    40    --    100   --     100                        prior art       2.0 100    100   80    40    100    100                                        4.0 100    100   90    100   100    100                        prior art       2.0 50     22    20    30    --     --                                         4.0 88     57    95    62    100    83                          ##STR164##                                                                    A                                                                              prior art       2.0 90     90    60    --    60     40                                         4.0 95     100   90    --    80     60                         __________________________________________________________________________      0 = no damage                                                                  100 = plants completely destroyed                                        

                  TABLE 6                                                          ______________________________________                                         Herbicidal action in Bermuda grass;                                            postemergence application in the greenhouse                                            Test plants and % damage                                                                      Amaranthus                                                                     retroflexus                                             Com-                   from rhizomes    Mercur-                                pound         Cynodon  (Bermuda  Cyperus                                                                               ialis                                  no.   kg/ha   dactylon grass)    difformis                                                                             annua                                  ______________________________________                                         14    1.0     10       100       93     98                                           2.0     --       100       98     98                                     145   1.0     0        --        100    100                                          2.0     0        --        --     100                                    82    1.0     10       25        100    100                                          2.0     20       40        --     100                                    prior 1.0     0        70        100    36                                     art   2.0     --       100       100    56                                     ______________________________________                                          0 = no damage                                                                  100 = plants completely destroyed                                        

                                      TABLE 7                                      __________________________________________________________________________     Selective herbicidal action in peas;                                           postemergence treatment in the greenhouse                                                Test plants and % damage                                             Compound  Pisum                                                                                Ipomoea                                                                              Matricaria                                                                           Setaria                                                                           Sinapis                                                                            Stellaria                                   no.   kg/ha                                                                              sativum                                                                             spp.  spp.  spp.                                                                               alba                                                                               media                                       __________________________________________________________________________     113   1.0 0    40    100   30  --  --                                                2.0 10   75    100   100 --  --                                          30    1.0 0    60    0     40  100 100                                               2.0 10   65    0     75  100 100                                         68    1.0 2    95    100   98  100 100                                               2.0 4    99    100   98  100 100                                         14    1.0 12   90    7     98  90  95                                                2.0 20   100   7     98  95  95                                          69    1.0 0    100   100   100 100 100                                               2.0 0    100   100   100 100 100                                         prior art                                                                            1.0 10   43    100   0   98  98                                                2.0 --   55    100   30  98  98                                          C                                                                              prior art                                                                            1.0 15   0     20    --  80  90                                                2.0 28   --    20    --  100 100                                         __________________________________________________________________________      0 = no damage                                                                   100 = plants completely destroyed                                       

                                      TABLE 8                                      __________________________________________________________________________     Selective herbicidal action in safflower;                                      postemergence application in the greenhouse                                    Com-    Test plants and % damage                                               pound   Carthamus                                                                            Amaranthus                                                                              Euphorbia                                                                            Mercurialis                                                                          Sesbania                                                                            Sida                                                                               Solanum                                                                             Xanthium                      no. kg/ha                                                                              tinctorius                                                                           retroflexus                                                                             geniculata                                                                           annua exaltata                                                                            spinosa                                                                            nigrum                                                                              pensylvani                    __________________________________________________________________________     144 1.0 0     100      100   100   100  100 100  100                               2.0 0     100      100   100   100  100 100  100                           28  1.0 --    100      50    30    98   --  --   --                                2.0 0     100      70    100   95   --  --   --                            17  1.0 --    0        60    100   90   --  --   100                               2.0 0     0        70    100   100  --  --   100                           14  1.0 0     100      90    98    95   100 82   89                                2.0 0     100      96    98    100  100 100  98                            30  1.0 0     88       85    100   95   --  20   30                                2.0 0     90       85    100   95   --  100  30                            __________________________________________________________________________      0 =  no damage                                                                 100 = plants completely destroyed                                        

                                      TABLE 9                                      __________________________________________________________________________     Selective herbicidal action; postemergence treatment in the greenhouse          ##STR165##                                                                    __________________________________________________________________________     Com-                                  Test plants and % damage                 pound                                                                              Substituents                      Daucus                                                                              Helianthus                                                                            Sorghum                                                                            Triticum                                                                            Zea                 no. R.sup.1                                                                           R.sup.2                                                                            R.sup.3  R.sup.4      kg/ha                                                                                carota                                                                             annuus                                                                                bicolor                                                                            aestivum                                                                            mays                __________________________________________________________________________      30                              1.0  0    0     0    10   10                                                   2.0  0    10    10   23   10                   41                              1.0  --   --    --   --   10                                                   2.0  --   --    --   0    20                  144                              1.0  --   15    --   0    0                                                    2.0  --   20    --   --   0                   149                              1.0  --   10    --   --   0                                                    2.0  --   30    --   --   0                   prior art D                                                                        CH.sub.3                                                                          CH.sub.3                                                                            ##STR166##                                                                              ##STR167##  1.0 2.0                                                                             -- --                                                                               -- -- -- --                                                                               0 0  -- --               prior  art E                                                                       CH.sub.3                                                                          CH.sub.3                                                                            ##STR168##                                                                             OH           1.0 2.0                                                                             -- --                                                                               -- -- -- --                                                                               -- --                                                                               -- --               A                                1.0  --   --    5    0    10                  prior                            2.0  --   --    5    0    10                  art                                                                            C                                1.0  30   100   0    12   10                  prior                            2.0  35   100   10   18   15                  art                                                                            __________________________________________________________________________     Test plants and % damage                                                       Compound                                                                              Echinochloa                                                                          Euphorbia                                                                            Ipomoea                                                                             Lamium                                                                               Mercurialis                                                                          Polygonum                                                                            Sesbania                                                                            Setaria                                                                             Sinapis                                                                             Stellaris             no.   crus galli                                                                            geniculata                                                                           spp. purpureum                                                                            annua persicaria                                                                           exaltata                                                                            spp. alba media                 __________________________________________________________________________      30   20     85    60   80    100   100   95   40   100  100                         27     85    65   80    100   100   95   75   100  100                    41   10     40    52   10    100   60    60   20   100  --                          10     50    100  20    100   90    60   40   100  --                    144   70     100   95   95    100   --    100  100  100  --                          100    100   95   95    100   --    100  100  --   --                    149   100    100   90   95    100   --    100  95   100  --                          100    100   100  95    100   --    100  95   100  --                    prior art                                                                            70     --    --   --    --    --    --   --   0    --                    D     80     --    20   --    30    --    --   --   25   --                    prior art                                                                            10     --    0    0     0     --    --   --   15   60                    E     --     --    0    0     0     --    --   --   45   60                    A     0      100   13   0     10    --    40   0    0    30                    prior art                                                                            0      100   15   0     50    --    50   20   0    45                    C     0      --    0    100   --    --    --   --   80   90                    prior art                                                                            0      --    --   100   --    --    --   --   100  100                   __________________________________________________________________________      0 = no damage                                                                  100 = plants completely destroyed                                        

                  TABLE 10                                                         ______________________________________                                         Herbicidal action in strawberries;                                             postemergence treatment in the greenhouse                                              Test plants and % damage                                               Com-          Fra-   Lamium Mercur-       Stell-                               pound         garia  amplexi-                                                                              ialis  Solanum                                                                               aria                                 no.   kg/ha   vesca  caure  annua  nigrum madia                                ______________________________________                                         30    2.0     20     100    100    100    100                                  14    1.0     0      100     98    100    100                                  82    0.5     0      30     100    100    100                                  144   1.0     20     60     100    --     100                                  123   1.0     10     60     100    100    100                                  113   1.0     20     100    100    --     100                                  194   1.0     0      100    100    100    100                                  ______________________________________                                          0 = no damage                                                                  100 = plants completely destroyed                                        

                                      TABLE 11                                     __________________________________________________________________________     Herbicidal action in peanuts and cotton;                                       postemergence application in the greenhouse                                            Test plants and % damage                                               Com-         Gossy-                   Echin-                                   pound   Arachia                                                                             pium Alopocurus                                                                           Amaranthus                                                                            Chenopodium                                                                           ochlo-                                                                              Ipomoea                                                                             Portulaca                                                                           Sesbania                                                                            Solanum              no. kg/ha                                                                              hypognea                                                                            hirsutum                                                                            myosuroides                                                                          retroflexus                                                                           album  crus galli                                                                          spp. oleracea                                                                            exaltata                                                                            nigrum               __________________________________________________________________________     67  1.0 10   0    90    100    100    60   100  100  100  100                  68  0.5 10   --   90    100    100    70   75   100  95   100                  69  0.5 10   0    95    50     100    40   75   100  60   100                  70  1.0 0    0    95    50     90     --   60   100  60   100                  198 1.0 20   20   95    50     100    95   90   100  100  100                  77  2.0 0    10   95    --     90     100  60   100  95   100                  21  1.0 0    0    60    --     100    --   100  --   --   --                   165 0.5 15   0    85    100    100    --   --   100  --   40                   106 0.5 10   15   90    100    90     --   --   70   --   --                   153 2.0 0    20   --    100    100    40   --   100  --   100                  154 0.5 5    20   80    100    100    70   80   100  95   100                  31  2.0 0    0    --    100    90     --   100  100  70   --                   160 1.0 0    0    95    100    100    100  --   100  100  100                  80  1.0 5    5    --    --     --     100  50   100  100  --                   161 0.5 15   0    100   --     100    90   --   100  100  100                  __________________________________________________________________________      0 = no damage                                                                  100 = plants completely destroyed                                        

                  TABLE 12                                                         ______________________________________                                         Herbicidal action on weeds; postemergence application                          in the greenhouse                                                                      Test plants and % damage                                                             Alo-                                                             Com-          pecurus                Sida Xanthium                             pound         myosur-  Ipomoea                                                                               Sesbania                                                                              spin-                                                                               pensyl-                              no.   kg/ha   oides    spp.   exaltata                                                                              osa  vanicum                              ______________________________________                                         29    1.0     95       83     100    100  100                                        2.0     100      88     100    100  100                                  161   2.0     100      85     100    100  60                                   82    2.0     98       82     100    60   100                                  162   1.0     94       65     90     --   90                                         2.0     98       65     100    --   90                                   89    1.0     90       100    80     60   40                                         2.0     95       100    100    100  90                                   164   2.0     95       90     100    --   80                                   105   2.0     95       --     100    90   80                                   68    2.0     94       93     98     100  50                                   71    2.0     95       100    100    100  --                                   106   2.0     95       90     80     80   --                                   165   2.0     95       100    100    100  --                                   144   1.0     50       95     100    100  100                                        2.0     80       95     100    100  100                                  149   1.0     70       90     100    100  40                                         2.0     80       100    100    100  100                                  ______________________________________                                          0 = no damage                                                                  100 = plants completely destroyed                                        

                                      TABLE 13                                     __________________________________________________________________________     Selective herbicidal action; postemergence application in the greenhouse               Test plants and % damage                                               Com-                                                                           pound   Triticum                                                                            Zea                                                                               Amaranthus                                                                            Chenopodium                                                                           Euphorbia                                                                            Matricaria                                                                           Sinapis                                                                             Sesbania                                                                            Solanum                    no. kg/ha                                                                              aestivum                                                                            mays                                                                              retroflexus                                                                           album  geniculata                                                                           spp.  alba exaltata                                                                            nigrum                     __________________________________________________________________________     202 0.5  5    5 100    100    100   100   100  100  100                            1.0 10   12 100    100    100   100   100  100  100                        151 0.5 0    -- --     100    100   100   100   90  100                            1.0 0    -- --     100    100   100   100  100  100                        __________________________________________________________________________

EXAMPLE 11

9 parts by weight of compound 1 is mixed with 1 parts by weight of N-methyl-α-pyrrolidone. A mixture is obtained which is suitable for application in the form of very fine drops.

EXAMPLE 12

20 parts by weight of compound 2 is dissolved in a mixture consisting of 80 parts by weight of xylene, 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide to 1 mole of oleic acid-N-monoethanolamide, 5 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, and 5 parts by weight of the adduct of 40 moles of ethylene oxide to 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and uniformly distributing it therein, an aqueous dispersion is obtained containing 0.02% by weight of the active ingredient.

EXAMPLE 13

20 parts by weight of compound 3 is dissolved in a mixture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 7 moles of ethylene oxide to 1 mole of isooctylphenol, and 10 parts by weight of the adduct of 40 moles of ethylene oxide to 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and finely distributing it therein, an aqueous dispersion is obtained containing 0.02% by weight of the active ingredient.

EXAMPLE 14

20 parts by weight of compound 1 is dissolved in a mixture consisting of 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction having a boiling point between 210° C. and 280° C., and 10 parts by weight of the adduct of 40 moles of ethylene oxide to 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and uniformly distributing it therein, an aqueous dispersion is obtained containing 0.02% by weight of the active ingredient.

EXAMPLE 15

20 parts by weight of compound 2 is well mixed with 3 parts by weight of the sodium salt of diisobutylnaphthalene-α-sulfonic acid, 17 parts by weight of the sodium salt of a lignin-sulfonic acid obtained from a sulfite waste liquor, and 60 parts by weight of powdered silica gel, and triturated in a hammer mill. By uniformly distributing the mixture in 20,000 parts by weight of water, a spray liquid is obtained containing 0.1% by weight of the active ingredient.

EXAMPLE 16

3 parts by weight of compound 3 is intimately mixed with 97 parts by weight of particulate kaolin. A dust is obtained containing 3% by weight of the active ingredient.

EXAMPLE 17

30 parts by weight of compound 4 is intimately mixed with a mixture consisting of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which has been sprayed onto the surface of this silica gel. A formulation of the active ingredient is obtained having good adherence.

EXAMPLE 18

40 parts by weight of compound 1 is intimately mixed with 10 parts of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate, 2 parts of silica gel and 48 parts of water. Dilution in 100,000 parts by weight of water gives an aqueous dispersion containing 0.04 wt% of active ingredient.

EXAMPLE 19

20 parts of compound 2 is intimately mixed with 2 parts of the calcium salt of dodecylbenzenesulfonic acid, 8 parts of a fatty alcohol polyglycol ether, 2 parts of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate and 68 parts of a paraffinic mineral oil. A stable oily dispersion is obtained. 

We claim:
 1. A pyrazole of the formula ##STR169## where R¹ is hydrogen,R² is hydrogen or lower alkyl, R³ is n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 3-methyl-2-butyl, pentyl-2 or pentyl-3 or one of said groups substituted by lower alkoxy or is a 5-, 6-, or 7-membered cycloalkyl, R⁴ is methoxycarbonyl, and R⁵ is hydrogen or methyl, and the agriculturally acceptable acid addition salts thereof. 